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Introduction to Process Design

054416 INTEGRATED PROCESS DESIGN

WEEK 1: INTRODUCTION
TO PROCESS DESIGN

Daniel R. Lewin
Department of Chemical

(c) Daniel R. Lewin


Engineering
1
Technion, Haifa, Israel

2
Introduction to Process Design
SCHEDULE – INTRODUCTION TO PROCESS DESIGN

 The Design Process


 What steps are involved in process
design?
 What are the principle environmental and
safety issues?
 Process Creation

(c) Daniel R. Lewin


 Systematic top-down approach to assist
you in preparing base-case designs
 Design Heuristics
 Helpful rules of thumb, and qualitative
guidelines to help you get a design 2
started
2
Introduction to Process Design
INTRODUCTION TO PROCESS DESIGN

THE DESIGN PROCESS

(c) Daniel R. Lewin


Daniel R. Lewin
Department of Chemical
Engineering
3
Technion, Haifa, Israel

2
Introduction to Process Design
THE DESIGN PROCESS - LEARNING OBJECTIVES
On completing this part of the course, you
should:
 Have an appreciation of the key steps
in carrying out a process design. This
course, as the course text, is organized
to teach how to implement these
steps.

(c) Daniel R. Lewin


 Be aware of the many kinds of
environmental issues and safety
considerations that are prevalent in
the design of a new chemical process.

2
Introduction to Process Design
SCHEDULE - THE DESIGN PROCESS
 Primitive Design Problems
 Steps in Designing and Retrofitting Chemical
Processes
 Assess Primitive Problem
 Process Creation - Development of Base Case
 Detailed Process Synthesis - Algorithmic Methods
 Process Controllability Assessment

(c) Daniel R. Lewin


 HAZOP/HAZAN
 Detailed Design, Sizing, Cost Estimation, Optimization
 Construction, Start-up and Operation
 Environmental Protection

Ref: Seider, Seader and Lewin (2004), Chapter 1 2


Introduction to Process Design
PRIMITIVE DESIGN PROBLEMS
 The design or retrofit of chemical processes begins with
the desire to produce profitably chemicals that satisfy
societal needs that arise in the broad spectrum of
industries that employ chemical engineers:
– petrochemicals – polymers
– petroleum products – coatings
– industrial gases – electronic materials

(c) Daniel R. Lewin


– foods – bio-chemicals
– pharmaceuticals – nano-materials

 Partly due to the growing awareness of the public,


many design projects involve the redesign, or
retrofitting, of existing chemical processes to solve
environmental problems and to adhere to stricter
standards of safety 6

2
Introduction to Process Design
ORIGIN OF DESIGN PROBLEMS
 Often, design  However, several well-
problems result from known products, like
the explorations of Teflon were discovered
chemists, biochemists, by accident.
and engineers in
research labs to satisfy
the desires of
customers to obtain

(c) Daniel R. Lewin


chemicals with
improved properties
for many applications.

2
Introduction to Process Design
ORIGIN OF DESIGN PROBLEMS
 In other cases, an inexpensive
source of a raw material(s)
becomes available
 Other design problems
originate when new markets
are discovered, especially in
developing countries

(c) Daniel R. Lewin


 Yet another source of design
projects is the engineer
himself, who often has a
strong inclination that a new
chemical or route to produce
an existing chemical can be 8
very profitable.
2
Introduction to Process Design
A TYPICAL PRIMITIVE DESIGN PROBLEM
Consider, the need to manufacture vinyl chloride (VC),
H Cl
C C
H H

A typical primitive problem statement is as follows:


“An opportunity has arisen to satisfy a new demand for
VC monomer (VCM), of 800 million pounds per year,
in a petrochemical complex on the Gulf Coast, given

(c) Daniel R. Lewin


that an existing plant owned by the company produces
one-billion pounds per year of this commodity
chemical.
Since VCM is an extremely toxic substance, it is
recommended that all new facilities be designed
carefully to satisfy governmental health and safety 9
regulations.”
2
Introduction to Process Design
A TYPICAL PRIMITIVE DESIGN PROBLEM
Consider, the need to manufacture vinyl chloride (VC),
H Cl
C C
H H

A typical primitive problem statement is as follows:


“An opportunity has arisen to satisfy a new demand for
VC monomer (VCM), of 800 million pounds per year,
in a petrochemical complex on the Gulf Coast, given

(c) Daniel R. Lewin


that an existing plant owned by the company produces
one-billion pounds per year of this commodity
chemical.
Since VCM is an extremely toxic substance, it is
recommended that all new facilities be designed
carefully to satisfy governmental health and safety 10
regulations.”
2
Introduction to Process Design
A TYPICAL PRIMITIVE DESIGN PROBLEM
Consider, the need to manufacture vinyl chloride (VC),
H Cl
C C
H H

A typical primitive problem statement is as follows:


“An opportunity has arisen to satisfy a new demand for
VC monomer (VCM), of 800 million pounds per year,
in a petrochemical complex on the Gulf Coast, given

(c) Daniel R. Lewin


that an existing plant owned by the company produces
one-billion pounds per year of this commodity
chemical.
Since VCM is an extremely toxic substance, it is
recommended that all new facilities be designed
carefully to satisfy governmental health and safety 11
regulations.”
2
Introduction to Process Design
A TYPICAL PRIMITIVE DESIGN PROBLEM
Consider, the need to manufacture vinyl chloride (VC),
H Cl
C C
H H

A typical primitive problem statement is as follows:


“An opportunity has arisen to satisfy a new demand for
VC monomer (VCM), of 800 million pounds per year,
in a petrochemical complex on the Gulf Coast, given

(c) Daniel R. Lewin


that an existing plant owned by the company produces
one-billion pounds per year of this commodity
chemical.
Since VCM is an extremely toxic substance, it is
recommended that all new facilities be designed
carefully to satisfy governmental health and safety 12
regulations.”
2
Introduction to Process Design
THE DESIGN PROCESS

STEPS IN PROCESS DESIGN

(c) Daniel R. Lewin


Daniel R. Lewin
Department of Chemical
Engineering
13
Technion, Haifa, Israel

2
Introduction to Process Design
STEPS IN PROCESS DESIGN AND RETROFIT

Assess Primitive
Problem

Detailed Process Plant-wide


Synthesis - Development Controllability
Algorithmic of Base-case and Safety
Methods

(c) Daniel R. Lewin


Assessment

Detailed Design,
Equipment sizing,
Cap. Cost Estimation,
Profitability Analysis,
Optimization
14

2
Introduction to Process Design
STEPS IN PROCESS DESIGN AND RETROFIT
SECTION A
Assess Primitive
Problem

Detailed Process Plant-wide


Synthesis - Development Controllability
Algorithmic of Base-case and Safety
Methods

(c) Daniel R. Lewin


Assessment

Detailed Design,
Equipment sizing,
Cap. Cost Estimation,
Profitability Analysis,
Optimization
15

2
Introduction to Process Design
ASSESS PRIMITIVE PROBLEM
 Process design begins with a primitive design problem
that expresses the current situation and provides an
opportunity to satisfy a societal need.
 Normally, the primitive problem is examined by a small
design team, who begins to assess its possibilities, to
refine the problem statement, and to generate more
specific problems:
 Raw materials - available in-house, can be purchased

(c) Daniel R. Lewin


or need to be manufactured?
 Scale of the process (based upon a preliminary
assessment of the current production, projected
market demand, and current and projected selling
prices)
 Location for the plant
 Refined through meetings with engineering technical
16
management, business and marketing.
 Brainstorming to generate alternatives
2
Introduction to Process Design
EXAMPLE: VC MANUFACTURE
To satisfy the need for an additional 800 MMlb/yr of VCM,
the following plausible alternatives might be generated:
 Alternative 1. A competitor’s plant, which produces 2
MMM lb/yr of VCM and is located about 100 miles away,
might be expanded to produce the required amount,
which would be shipped. In this case, the design team
projects the purchase price and designs storage facilities.
 Alternative 2. Purchase and ship, by pipeline from a

(c) Daniel R. Lewin


nearby plant, chlorine from the electrolysis of NaCl
solution. React the chlorine with ethylene to produce the
monomer and HCl as a byproduct.
 Alternative 3. Since the existing company produces HCl
as a byproduct in large quantities are produced, HCl is
normally available at low prices. Reactions of HCl with
acetylene, or ethylene and oxygen, could produce 1,2- 17
dichloroethane, an intermediate that can be cracked to
produce vinyl chloride. 2
Introduction to Process Design
SURVEY LITERATURE SOURCES
 SRI Design Reports
 Encyclopedias
 Kirk-Othmer Encyclopedia of Chemical
Technology (1991)
 Ullman’s Encyclopedia of Industrial Chemistry
(1988)
 ...

(c) Daniel R. Lewin


 Handbooks and Reference Books
 Perry’s Chemical Engineers Handbook (1997)
 CRC Handbook of Chemistry and Physics
 ...
 Indeces (plural of index)
 See Technion Library
 Patents 18
 Internet
2
Introduction to Process Design
STEPS IN PROCESS DESIGN AND RETROFIT

Assess Primitive
Problem

Detailed Process Plant-wide


Synthesis - Development Controllability
Algorithmic of Base-case and Safety
Methods

(c) Daniel R. Lewin


Assessment

Detailed Design,
Equipment sizing,
Cap. Cost Estimation, SECTION B
Profitability Analysis,
Optimization
19

2
Introduction to Process Design
STEPS IN PROCESS DESIGN AND RETROFIT

Assess Primitive
Problem

Detailed Process Plant-wide


Synthesis - Development Controllability
Algorithmic of Base-case and Safety
Methods

(c) Daniel R. Lewin


Assessment

SECTION C
Detailed Design,
Equipment sizing,
Cap. Cost Estimation,
Profitability Analysis,
Optimization
20

2
Introduction to Process Design
STEPS IN PROCESS DESIGN AND RETROFIT

Assess Primitive
Problem

Detailed Process Plant-wide


Synthesis - Development Controllability
Algorithmic of Base-case and Safety
Methods

(c) Daniel R. Lewin


Assessment

SECTION D
Detailed Design,
Equipment sizing,
Cap. Cost Estimation,
Profitability Analysis,
Optimization
21

2
Introduction to Process Design
THE DESIGN PROCESS

INTRODUCTION TO
ENVIRONMENTAL ISSUES
IN PROCESS DESIGN

(c) Daniel R. Lewin


Daniel R. Lewin
22
Department of Chemical
Engineering
Technion, Haifa, Israel

2
Introduction to Process Design
ENVIRONMENTAL ISSUES IN PROCESS DESIGN
 Handling of toxic wastes
 97% of hazardous waste generation by the chemicals and
nuclear industry is wastewater (1988 data).
 In process design, it is essential that facilities be included
to remove pollutants from wastewater streams.
 Reaction pathways to reduce by-product toxicity
 As the reaction operations are determined, the toxicity of
all of the chemicals, including those recovered as
byproducts, needs to be evaluated.

(c) Daniel R. Lewin


 Pathways involving large quantities of toxic chemicals
should be replaced by alternatives, except under unusual
circumstances.
 Reducing and reusing wastes
 Environmental concerns place even greater emphasis on
recycling, not only for unreacted chemicals, but for product
and by-product chemicals, as well. (i.e., production of
23
segregated wastes - e.g., production of composite materials
and polymers).
2
Introduction to Process Design
ENVIRONMENTAL ISSUES IN PROCESS DESIGN
 Avoiding non-routine events
 Reduce the likelihood of accidents and spills through the
reduction of transient phenomena, relying on operation at
the nominal steady-state, with reliable controllers and
fault-detection systems.
 Design objectives, constraints and optimization
 Environmental goals often not well defined because
economic objective functions involve profitability

(c) Daniel R. Lewin


measures, whereas the value of reduced pollution is often
not easily quantified economically.
 Solutions: mixed objective function (“price of reduced
pollution”), or express environmental goal as “soft” or
“hard” constraints.
 Environmental regulations = constraints

24

2
Introduction to Process Design
THE DESIGN PROCESS

INTRODUCTION TO
SAFETY ISSUES IN
PROCESS DESIGN

(c) Daniel R. Lewin


Daniel R. Lewin
25
Department of Chemical
Engineering
Technion, Haifa, Israel

2
Introduction to Process Design
SAFETY ISSUES: FIRES AND EXPLOSIONS
Flammability Limits of Liquids and Gases
LFL and UFL (vol %) in Air at 25 oC and 1 Atm
Compound LFL (%) UFL (%)
Acetylene 2.5 100
Cyclohexane 1.3 8
Ethylene 2.7 36
Ethylene Oxide 3.0 100

(c) Daniel R. Lewin


Gasoline 1.4 7.6
Hydrogen 4.0 75

These limits can be extended for mixtures, and for


elevated temperatures and pressures (see Seider et al,
2004).
With this kind of information, the process designer makes 26
sure that flammable mixtures do not exist in the process
during startup, steady-state operation, or shut-down. 2
Introduction to Process Design
DESIGN APPROACHES FOR SAFETY
 Techniques to Prevent Fires and Explosions
 Inerting - addition of inert dilutant to reduce the
fuel concentration below the LFL
 Installation of grounding devices and anti-static
devices to avoid the buildup of static electricity
 Use of explosion proof equipment
 Ensure ventilation - install sprinkler systems

(c) Daniel R. Lewin


 Relief Devices
 Hazard Identification and Risk Assessment
 Carry out a Hazard and Operability (HAZOP)
study, to identify all of the possible paths to an
accident.
 Create a fault tree, and estimate the probability 27
of the occurrence for each potential accident
(when data is available). 2
Introduction to Process Design
THE DESIGN PROCESS - SUMMARY
 Steps in Designing and Retrofitting Chemical
Processes
 Assess Primitive
Assess Primitive Problem – Just completed 
Problem
ProcessCreation
 Process Creation – Tomorrow!
 Detailed Process Synthesis - Algorithmic Methods
 Process Controllability Assessment
 HAZOP/HAZAN

(c) Daniel R. Lewin


 Detailed Design, Sizing, Cost Estimation, Optimization
 Construction, Start-up and Operation
 Environmental Protection
 Environmental regulations are design constraints
 Safety Considerations
 Should strive to design “inherently safe plants”
28

2
Introduction to Process Design
CLASS QUIZ 1.1
Which of the following is not specified in the
definition of a primitive design problem?
A. The chemical that needs to be produced.
B. The amount per year of the chemical that
needs to be produced.
The desired geographical location where

(c) Daniel R. Lewin


C.
the chemical needs to be produced.
D. The process to be used to make the
chemical that needs to be produced.

29

2
Introduction to Process Design
A TYPICAL PRIMITIVE DESIGN PROBLEM
Consider, the need to manufacture vinyl chloride (VC),
H Cl
C C
H H

A typical primitive problem statement is as follows:


“An opportunity has arisen to satisfy a new demand for
VC monomer (VCM), of 800 million pounds per year,
in a petrochemical complex on the Gulf Coast, given

(c) Daniel R. Lewin


that an existing plant owned by the company produces
one-billion pounds per year of this commodity
chemical.
Since VCM is an extremely toxic substance, it is
recommended that all new facilities be designed
carefully to satisfy governmental health and safety 30
regulations.”
2
Introduction to Process Design
A TYPICAL PRIMITIVE DESIGN PROBLEM
Consider, the need to manufacture vinyl chloride (VC),
H Cl
C C
H H

A typical primitive problem statement is as follows:


“An opportunity has arisen to satisfy a new demand for
VC monomer (VCM), of 800 million pounds per year,
in a petrochemical complex on the Gulf Coast, given

(c) Daniel R. Lewin


that an existing plant owned by the company produces
one-billion pounds per year of this commodity
chemical.
Since VCM is an extremely toxic substance, it is
recommended that all new facilities be designed
carefully to satisfy governmental health and safety 31
regulations.”
2
Introduction to Process Design
A TYPICAL PRIMITIVE DESIGN PROBLEM
Consider, the need to manufacture vinyl chloride (VC),
H Cl
C C
H H

A typical primitive problem statement is as follows:


“An opportunity has arisen to satisfy a new demand for
VC monomer (VCM), of 800 million pounds per year,
in a petrochemical complex on the Gulf Coast, given

(c) Daniel R. Lewin


that an existing plant owned by the company produces
one-billion pounds per year of this commodity
chemical.
Since VCM is an extremely toxic substance, it is
recommended that all new facilities be designed
carefully to satisfy governmental health and safety 32
regulations.”
2
Introduction to Process Design
A TYPICAL PRIMITIVE DESIGN PROBLEM
Consider, the need to manufacture vinyl chloride (VC),
H Cl
C C
H H

A typical primitive problem statement is as follows:


“An opportunity has arisen to satisfy a new demand for
VC monomer (VCM), of 800 million pounds per year,
in a petrochemical complex on the Gulf Coast, given

(c) Daniel R. Lewin


that an existing plant owned by the company produces
one-billion pounds per year of this commodity
chemical.
Since VCM is an extremely toxic substance, it is
recommended that all new facilities be designed
carefully to satisfy governmental health and safety 33
regulations.”
2
Introduction to Process Design
INTRODUCTION TO PROCESS DESIGN

PROCESS CREATION

(c) Daniel R. Lewin


Daniel R. Lewin
Department of Chemical
Engineering
34
Technion, Haifa, Israel

2
Introduction to Process Design
PROCESS CREATION - LEARNING OBJECTIVES
On completing this part of the course, you
should:
 Understand how to go about assembling design
data and creating a preliminary data base.
 Be able to implement the steps in creating
flowsheets involving reactions, separations, and

(c) Daniel R. Lewin


T-P change operations. In so doing, many
alternatives are identified that can be assembled
into a synthesis tree that contains the most
promising alternatives.
 Know how to select the principal pieces of
equipment and to create a detailed process
35
flowsheet, with a material and energy balance
and a list of major equipment items.
2
Introduction to Process Design
SCHEDULE - PROCESS CREATION
 Preliminary Database Creation
 To assemble data to support the design.
 Experiments
 often necessary to supply missing database
items or verify crucial data.
 Preliminary Process Synthesis
 top-down approach.

(c) Daniel R. Lewin


 To generate a “synthesis tree” of design
alternatives.
 illustrated by the synthesis of processes for
the manufacture of VCM.
 Development of Base-case Design
 focusing on the most promising alternative(s)
from the synthesis tree. 36

Ref: Seider, Seader and Lewin (2004), Chapter 3 2


Introduction to Process Design
PRELIMINARY DATABASE CREATION
 Thermophysical property data
 physical properties
 phase equilibria (VLE data)
 Property prediction methods
 Environmental and safety data
 toxicity data
flammability data

(c) Daniel R. Lewin


 Chemical Prices
 e.g. as published in the Chemical Marketing Reporter
 Experiments
 to check on crucial items above

37

2
Introduction to Process Design
PRELIMINARY PROCESS SYNTHESIS
Synthesis of chemical processes involves:
 Selection of processing mode: continuous or batch
 Fixing the chemical state of raw materials, products,
and by-products, noting the differences between
them.
 Process operations (unit operations) - flowsheet
building blocks
 Synthesis steps -

(c) Daniel R. Lewin


 Eliminate differences in molecular types

 Distribute chemicals by matching sources and sinks

 Eliminate differences in composition

 Eliminate differences in temperature, pressure and


phase
38
 Integrate tasks (combine tasks into unit operations)
2
Introduction to Process Design
CONTINUOUS OR BATCH PROCESSING?

Continuous

Batch

(c) Daniel R. Lewin


Fed-batch

Batch-product removal
39

2
Introduction to Process Design
THE CHEMICAL STATE

Decide on the raw material and product specifications


(states):
 Mass (flow rate, if continuous)

(c) Daniel R. Lewin


 Composition (mole or mass fraction of each
chemical species having a unique molecular type)
 Phase (solid, liquid, or gas)
 Form (e.g., particle-size distribution and particle
shape)
 Temperature
40
 Pressure
2
Introduction to Process Design
PROCESS OPERATIONS (“LEGO”)
 Chemical reaction
 Positioning in the flowsheet involves
many considerations (conversion, rates,
etc.), related to T and P at which the
reaction are carried out.
 Separation of chemicals
 Needed to resolve difference between

(c) Daniel R. Lewin


the desired composition of a product
stream and that of its source. Selection
of the appropriate method depends on
the differences of the physical properties
of the chemical species involved.
 Phase separation
 Change of temperature, pressure and phase
41
 Mixing and splitting of streams and
branches 2
Introduction to Process Design
SYNTHESIS STEPS

Synthesis Step Process Operation


 Eliminate differences in Chemical reaction
molecular types
 Distribute chemicals by
Mixing
matching sources and

(c) Daniel R. Lewin


sinks
 Eliminate differences in Separation
composition
 Eliminate differences in Temperature, pressure
temperature, pressure and and phase change
phase
42
 Integrate tasks (combine
tasks into unit operations) 2
Introduction to Process Design
PROCESS CREATION

EXAMPLE:
VINYL CHLORIDE MANUFACTURE

(c) Daniel R. Lewin


Daniel R. Lewin
Department of Chemical
43
Engineering
Technion, Haifa, Israel

2
Introduction to Process Design
 ELIMINATE DIFFERENCES IN MOLECULAR TYPE

Chemicals participating in VC Manufacture:


Molecular Chemical Chemical
Chemical weight formula structure
Acetylene 26.04 C2H2 H-CC-H

Chlorine 70.91 Cl2 Cl-Cl


Cl Cl
| |
1,2- 98.96 C2H4Cl2

(c) Daniel R. Lewin


H-C-C-H
Dichloroethane | |
H H
H H
Ethylene 28.05 C2H4 C=C
H H

Hydrogen 36.46 HCl H-Cl


chloride
H Cl
Vinyl chloride 62.50 C2H3Cl C=C 44
H H

2
Introduction to Process Design
SELECTION OF PATHWAY TO VCM
 Direct chlorination of ethylene:
C2H4 + Cl2  C2H3Cl + HCl

Advantages:
– Attractive solution to the specific problem
denoted as Alternative 2 in analysis of primitive
problem.

(c) Daniel R. Lewin


– Occurs spontaneously at a few hundred oC.
Disadvantages:
– Does not give a high yield of VC without
simultaneously producing large amounts of by-
products such as dichloroethylene.
– Half of the expensive chlorine is consumed to
produce HCl by-product, which may not be sold 45
easily.
2
Introduction to Process Design
SELECTION OF PATHWAY TO VCM
 Hydrochlorination of acetylene:
C2H2 + HCl  C2H3Cl
Advantages:
– This exothermic reaction is a potential solution
for the specific problem denoted as Alternative 3.
It provides a good conversion (98%) of C2H2 VC

(c) Daniel R. Lewin


in the presence of HgCl2 catalyst impregnated in
activated carbon at atmospheric pressure.
– These are fairly moderate reaction conditions,
and hence, this reaction deserves further study.
Disadvantages:
– Flammability limits of C2H2 (2.5 100%).
46

2
Introduction to Process Design
SELECTION OF PATHWAY TO VCM
 Thermal cracking of C2H4Cl2 from chlorination of C2H4:
C2H4 + Cl2  C2H4Cl2
C2H4Cl2  C2H3Cl + HCl
C2H4 + Cl2  C2H3Cl + HCl
Advantages:
– Conversion of ethylene to 1,2-dichloroethane in the 1st

(c) Daniel R. Lewin


(exothermic) reaction is 98% at 90 oC and 1 atm with a
Friedel-Crafts catalyst such as FeCl3. This intermediate is
converted to vinyl chloride by thermal cracking according
to the 2nd (endothermic) reaction, which occurs
spontaneously at 500 oC with conversions as high as
65% (Alternative 2).
Disadvantage: 47
– Half of the expensive chlorine is consumed to produce
HCl by-product, which may not be sold easily. 2
Introduction to Process Design
SELECTION OF PATHWAY TO VCM
 Thermal Cracking of C2H4Cl2 from Oxychlorination
of C2H4:
C2H4 + 2HCl + 12 O2  C2H4Cl2 + H2O
C2H4Cl2  C2H3 Cl + HCl
1
C2H4 + HCl + 2
O2  C2H3Cl + H2O

(c) Daniel R. Lewin


Advantages:
– Highly exothermic first reaction achieves a 95%
conversion to C2H4Cl2 in the presence of CuCl2 catalyst,
followed by pyrolysis step as in Reaction Path 3.
– Excellent candidate when cost of HCl is low
– Solution for specific problem denoted as Alternative 3.
Disadvantages: 48

─ Economics dependent on cost of HCl


2
Introduction to Process Design
SELECTION OF PATHWAY TO VCM
 Balanced Process for Chlorination of Ethylene:
C2H4 + Cl2  C2H4Cl2
C2H4 + 2HCl + 12 O2  C2H4Cl2 + H2O
2C2H4Cl2  2C2H3 Cl + 2HCl
2 C2H4 + Cl2 + 12 O2  2 C2H3Cl + H2O

(c) Daniel R. Lewin


Advantages:
– Combination of Reaction Paths 3 and 4 - addresses
Alternative 2.
– All Cl2 converted to VC
– No by-products!

49

2
Introduction to Process Design
EVALUATION OF ALTERNATIVE PATHWAYS
 Reaction Path  is eliminated due its low selectivity.
 This leaves four alternative paths, to be compared first
in terms of Economic Potential.

Chemical Bulk Prices


Chemical Cost (cents/lb)
Ethylene 18

(c) Daniel R. Lewin


Acetylene 50
Chlorine 11
Vinyl chloride 22
Hydrogen chloride 18
Water 0
Oxygen (air) 0

50

2
Introduction to Process Design
COMPUTING THE ECONOMIC POTENTIAL
Reaction path  C 2H 4 + Cl2 = C2H3Cl + HCl
lb-mole 1 1 1 1
Molecular weight 28.05 70.91 62.50 36.46
lb 28.05 70.91 62.50 36.46
lb/lb of vinyl chloride 0.449 1.134 1 0.583
cents/lb 18 11 22 18

EP = 22(1) + 18(0.583) - 18(0.449) - 11(1.134) = 11.94 cents/lb VC

(c) Daniel R. Lewin


Reaction Economic Potential
Overall Reaction
Path (cents/lb of VC)
 C2H2 + HCl = C2H3Cl -9.33

 C2H4 +Cl2 = C2H3Cl + HCl 11.94

 C2H4 + HCl + O2 = C2H3Cl + H2O 3.42

2C2H4 + Cl2 + O2 = 2C2H3Cl + H2O 7.68 51


2
Introduction to Process Design
PRELIMINARY FLOWSHEET FOR PATH 
Cl2 HCl
113,400 lb/hr 58,300 lb/hr
C2H4Cl2
Raw MaterialsDirect Products
HCl
Pyrolysis
Chlorination Process Flowsheet?
C2H3Cl
C2H4, Cl2 C2C H32 Cl,
H24Cl HCl
C2H3Cl
C2H4 C2H4 + Cl2 C2H4Cl2 C2H4Cl2  C2H3Cl + HCl
100,000 lb/hr
44,900 lb/hr

(c) Daniel R. Lewin


 800 MM lb/year @ 330 days/y  100,000 lb/hr VC
 On the basis of this principal sink, the HCl sink and
reagent sources can be computed (each flow is 1,600
lbmol/h)
 Next step involves distributing the chemicals by 52
matching sources and sinks.
2
Introduction to Process Design
 DISTRIBUTE THE CHEMICALS
 A conversion of 100% of the C2H4 is assumed in the
chlorination reaction.

(c) Daniel R. Lewin


53

2
Introduction to Process Design
 DISTRIBUTE THE CHEMICALS
 Only 60% of the C2H4Cl2 is converted to C2H3Cl with a
byproduct of HCl.
 To satisfy the overall material balance, 158,300 lb/h of
C2H4Cl must produce 100,000 lb/h of C2H3Cl and 58,300
lb/h of HCl.
 But a 60% conversion only produces 60,000 lb/h of VC.

(c) Daniel R. Lewin


 The additional C2H4Cl2 needed is computed by mass
balance to equal:
[(1 - 0.6)/0.6] x 158,300 or 105,500 lb/h.
 Its source is a recycle stream from the separation of
C2H3Cl from unreacted C2H4Cl2, from a mixing operation,
inserted to combine the two sources, to give a total of 54
158,300 + 105,500 = 263,800 lb/h.
2
Introduction to Process Design
 DISTRIBUTE THE CHEMICALS
 The effluent stream from the pyrolysis operation is the
source for the C2H3Cl product, the HCl by-product, and the
C2H4Cl2 recycle.

(c) Daniel R. Lewin


55
Introduction to Process Design
 DISTRIBUTE THE CHEMICALS
Reactor pressure levels:
 Chlorination reaction: 1.5 atm is recommended, to
eliminate the possibility of an air leak into the reactor
containing ethylene.
 Pyrolysis reaction: 26 atm is recommended by the
B.F. Goodrich patent (1963) without any justification.
Since the reaction is irreversible, the elevated
pressure does not adversely affect the conversion.

(c) Daniel R. Lewin


Most likely, the patent recommends this pressure to
reduce the size of the pyrolysis furnace, although the
tube walls must be considerably thicker and many
precautions are necessary for operation at elevated
pressures.
 The pressure level is also an important consideration
in selecting the separation operations, as will be 56

discussed in the next synthesis step.


2
Introduction to Process Design
 ELIMINATE DIFFERENCES IN COMPOSITION
 The product of the chlorination reaction is nearly pure
C2H4Cl2, and requires no purification.
 In contrast, the pyrolysis reactor conversion is only 60%,
and one or more separation operations are required to
match the required purities in the C2H3Cl and HCl sinks.
 One possible arrangement is given in the next slide. The
data below explains the design decisions made.

(c) Daniel R. Lewin


Boiling point (oC) Critical constants

Chemical 1 atm 4.8 atm 12 atm 26 atm Tc,C Pc, atm


HCl -84.8 -51.7 -26.2 0 51.4 82.1
C2H3Cl -13.8 33.1 70.5 110 159 56
57
C2H4Cl2 83.7 146 193 242 250 50

2
Introduction to Process Design
Boiling point (oC) Critical constants

ELIMINATE
Chemical 1 atm D4.8
IFFERENCES IN
atm 12 atm 26 COMPOSITION
atm T ,C P , atm
c c

HCl -84.8 -51.7 -26.2 0 51.4 82.1


C2H3Cl -13.8 33.1 70.5 110 159 56
C2H4Cl2 83.7 146 193 242 250 50

(c) Daniel R. Lewin


58
There may be alternative, and possibly better,
configurations, as discussed in Week 5.
2
Introduction to Process Design (c) Daniel R. Lewin
2
59
 ELIMINATE DIFFERENCES IN P, T AND PHASE
Introduction to Process Design (c) Daniel R. Lewin
2
 INTEGRATE TASKS (TASKUNIT OPERATIONS)

60
Introduction to Process Design
ASSEMBLY OF SYNTHESIS TREE
Reaction Distribution Separations T, P and Task
path of chemicals phase integration
changes


(c) Daniel R. Lewin



Algorithmic methods are very effective for the
61
synthesis, analysis and optimization of alternative
flowsheets. These will be covered in Section C
2
Introduction to Process Design
DEVELOPMENT OF BASE-CASE DESIGN
Develop one or two of the more promising flowsheets from
the synthesis tree for more detailed consideration.

(c) Daniel R. Lewin


62

2
Introduction to Process Design
PROCESS CREATION - SUMMARY
 Preliminary Database Creation
 needed to provide data to support the design.
 Experiments
 often necessary to supply missing database
items or verify crucial data.
 Preliminary Process Synthesis
 top-down approach.

(c) Daniel R. Lewin


 generates a “synthesis tree” of design
alternatives.
 illustrated by the synthesis of the VCM
process.
 Development of Base-case Design
 focusing on the most promising alternative(s)
from the synthesis tree. 63

2
Introduction to Process Design
CLASS QUIZ 1.2
Which are following is not a reason to eliminate
a potential chemical path to a desired product
from consideration for a new process?
A. The economic potential is negative.
B. The selectivity of the chemical path is too
low.

(c) Daniel R. Lewin


C. The chemical path uses a chemical with
LFL=1% and UFL=99%.
D. The chemical path appears to require too
many steps.
64

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